Method of washing soiled culinary articles

ABSTRACT

Soiled culinary articles are washed with an aqueous composition containing water and a catalytically effective amount of a novel catalyst. The invention is especially effective in washing soiled culinary articles which have food deposits and other foreign materials adhering tightly to the surface thereof. When desirable, the aqueous composition may also contain a surface active agent or a combination of a surface active agent and a water softening agent. The novel catalyst which is used in preparing the aqueous composition is prepared by steps including admixing a water soluble alkali metal silicate with an aqueous medium containing carefully controlled amounts of dissolved water soluble substances which are sources of calcium ion and magnesium ion, reacting the same to produce an aqueous finely divided or colloidal suspension of the reaction product, admixing a micelleforming surfactant with the aqueous medium, and agitating the aqueous medium containing the finely divided or colloidal particles and surfactant to form catalyst-containing micelles.

United States Patent Willard, Sr.

[ METHOD OF WASHING SOILED CULINARY ARTICLES John W. Willard, Sr., RapidCity, S. Dak.

[73] Assignee: CAW Industries, Inc., Rapid City, S.

Dak.

[22] Filed: Aug. 16, 1973 {21] Appl. No.: 388,776

Related U.S. Application Data [63] Continuation-impart of Ser. No.317,097, Dec. 20, 1972, which is a continuation of Ser. No. 108,198,Jan. 20, 1971, abandoned.

[75] Inventor:

[52] U.S. Cl. 134/25 A, 134/25 R, 134/40, 252/109, 252/135, 252/313 S,252/449,

{51] lnt. Cl B08b 3/08 {58] Field of Search..... 252/428, 429 B, 449,313 S, 252/532, 451, 454, 457, 455 R, 452, 109,

D10. 10; 134/25 R, 25 A, 40

[ Apr. 1, 1975 3,708,428 1/1973 McDonald 252/109 Primary Examiner-RobertL. Lindsay, Jr. Assistant Examiner-Marc L. Caroff Attorney, Agent, orFirmL. S. Van Landingham, .Ir.

[5 7] ABSTRACT Soiled culinary articles are washed with an aqueouscomposition containing water and a catalytically effective amount of anovel catalyst. The invention is especially effective in washing soiledculinary articles which have food deposits and other foreign materialsadhering tightly to the surface thereof. When desirable, the aqueouscomposition may also contain a surface active agent or a combination ofa surface active agent and a water softening agent. The novel catalystwhich is used in preparing the aqueous composition is prepared by stepsincluding admixing a water soluble alkali metal silicate with an aqueousmedium containing carefully controlled amounts of dissolved watersoluble substances which are sources of calcium ion and magnesium ion,reacting the same to produce an aqueous finely divided or colloidalsuspension of the reaction product, admixing a micelle-formingsurfactant with the aqueous medium, and agitating the aqueous mediumcontaining the finely divided or colloidal particles and surfactant toform catalyst-containing micelles.

37 Claims, No Drawings METHOD OF WASHING SOILED CULINARY ARTICLESRELATED APPLICATIONS This application is a continuation-in-part ofcopending application Ser. No. 317,097, filed Dec. 20, 1972, on behalfof John W. Willard, Sr., for Novel Catalyst and Process For PreparingThe Same. Application Ser. No. 3l7,097, in turn, is a continuation ofapplication Ser. No. l08,198 filed Jan. 20, 1971, now abandoned. Thedisclosures of applications Ser. Nos. 108,198 and 3l7.097 areincorporated herein by reference.

BACKGROUND OF THE INVENTION This invention relates to a novel method ofwashing soiled culinary articles. The invention is especially useful inremoving tightly adhering food deposits and foreign materials in generalfrom the surface of soiled culinary articles.

A large number of surface active agents have been used heretofore informulating dishwashing detergents. Examples include the alkali metalsoaps of long chain fatty acids. the alkali metal soaps of rosin acidsand the derivatives of rosin acids, synthetic detergents of the anionic,cationic or nonionic types and mixtures of one or more of thesesubstances. It has been common practice to use inert diluents such assodium sulfate, or builders such as polyphosphates, polysilicates orsodium carboxymethylcellulose in combination with one or more surfaceactive agents. A number of nitrogencontaining sequestering agents,anti-bacterial agents, bleaching agents and water softening agents alsohave been added to dishwashing detergents heretofore.

The commercially available prior art detergent compositions recommendedfor washing dishes and other culinary articles are not entirelysatisfactory for a number of reasons. For instance, dishwashingdetergents widely used at the present time often include a phosphorousor nitrogencontaining compound which either directly or indirectlyresults in a pollution problem. The phosphorous and nitrogen-containingcompounds promote the growth of microorganisms and alga in streams andother bodies of water into which sewage is introduced and this resultsin an adverse change in the ecology. The presence of a highconcentration of sodium sulfate and other soluble fillers is undesirablewhen the water is to be reused down stream for purposes which require alow sodium or solubles content. In instances where the prior artdishwashing detergents contain synthetic surfactants which are notdestroyed by microorganisms at a sufficiently rapid rate, the surfactantconcentration in streams also tends to increase to an objectionablelevel.

Many of the prior art dishwashing detergents are not sufficiently fastacting to remove tightly adhering food deposits and/or food stainswithin the period of time available when washing dishes in modernautomatic dishwasher. As a result, dried food deposits and thermallydecomposed food deposits on burned or scorched culinary articles are notremoved effectively. Also. food stains resulting from tea, coffee,fruits and the like are not removed effectively even in the presence ofstrong bleaching agents which often tend to destroy colored designs ondishes and chemically attack metallic culinary articles.

The prior art dishwashing detergents often have still otherdisadvantages such as requiring hot water for effective cleaning actionand tending to produce excessive suds and especially if too much isadded inadvertently to an automatic dishwasher. Many dishwashingdetergents also leave unsightly films or residua on the surface of thewashed and dried culinary articles.

In view of the foregoing, the prior art has long sought an entirelysatisfactory method of washing culinary articles which overcomes theabove mentioned and other well known deficiencies of presently useddishwashing detergents. However, an entirely satisfactory method ofwashing soiled culinary articles was not available prior to the presentinvention in spite of the long standing need.

It is an object of the present invention to provide a novel method ofwashing soiled culinary articles having food deposits adhering to thesurface thereof comprising intimately contacting the same with watercontaining a catalytically effective amount of a unique catalyst to bedescribed more fully hereinafter.

It is a further object to provide a novel method of washing soiledculinary articles wherein the culinary articles are intimately contactedwith an aqueous composition containing water, a surface active agentand/or a water softening agent in the presence of a catalyticallyeffective amount of the catalyst of the invention.

Still other objects and advantages will be apparent to those skilled inthe art upon reference to the following detailed description and thespecific examples illustrating the present invention.

DETAILED DESCRIPTION OF THE INVENTION INCLUDING PREFERRED VARIANTSTHEREOF In accordance with the present invention,soiled culinaryarticles are washed in an aqueous composition containing water and acatalytically effective amount of a novel catalyst to be described morefully hereinafter. The aqueous composition may contain a surface activeagent, or a combination of a surface active agent and a water softeningagent when desired. Other prior art additives for dishwashing detergentsalso may be present but usually they are not necessary and in someinstances undesirable.

In instances where the aqueous composition also contains a surfaceactive agent, it may be selected from the surface active agents used inwashing culinary articles in accordance with prior art practice.Examples of surface active agents include the alkali metal soaps of longchain fatty acids and especially the sodium and potassium soaps of fattyacids containing 14-25 carbon atoms and preferably about 16-18 carbonatoms. Other surface active agents include detergents which are notderived directly from fatty acids such as synthetic anionic, cationicand nonionic detergents. Specific examples of synthetic anionicdetergents include the alkali metal salts of organic sulfonates ororganic sulfates, and especially the alkali metal salts of highmolecular weight alkyl or alkylaryl sulfonates such as sodium orpotassium dodecyl benzene sulfonate, and the sodium and potassiumsulfates of fatty alcohols or products of the 0x0 process. Specificexamples of cationic detergents include the quaternary ammonium halidessuch as benzethonium chloride, and often members of this group haveoutstanding germicidal activity as well as surface active properties.Specific examples of nonionic detergents include compounds having apolyoxyethylene or other oxygenated side chain and the remainder of themolecule may be derived from fatty acids, alcohols. phenols, amides oramines.

Further examples of surface active agents are disclosed in the sectionon detergency appearing in the Kirk-Othmer Encyclopedia of ChemicalTechnology (2nd Edition). Volume 6. pages 853895. the disclosure ofwhich is incorporated herein by reference. Still additional specificexamples of detergent compositions are found in numerous US. patents.including the followmg which are incorporated herein by reference:

3.031.510 3.118.000 3.2212147 3.3211177 3.043.780 3.1 19.848 3.223.6473.382.285 3.048.548 3.l4U.26l 3.2141245: 3.421021 3.053.771 3.144.4123.3141191 3.424.689 3.061.55l 3.50.055 3.320172 3.429.822 3.067 1433.l73.877 3.326.807 3.437.697 3.082.172 3.203.955 3.337.463 3.444.2423.095.381 3.208.949 1.349.038 3.499.841 3.101.297 3.2l3.028 3.359.2053.507.798 3.101.374 3.213.633 3.38 .176

It is understood that the above surface active agents are given by wayof example only. and that other suitable surface active agents may beused. A mixture of one or more of the above surface active agents may beused when desired.

In instances where the aqueous composition also contains a watersoftening agent. it likewise may be selected from the water softeningagents used in washing culinary articles in accordance with prior artpractice. Examples of water softening agents include washing soda.trisodium phosphate. sodium metaphosphate. sodium tetraphosphate andother substances effective to remove calcium and/or magnesium ions fromwater. Mixtures of water softening agents may be used. The watersoftening agent may be employed in the usual amount necessary to softenthe water content of the aqueous composition.

The water used in preparing the aqueous composition for use in washingthe soiled culinary articles may be untreated or softened tap waterderived from municipal water sources. wells or springs. A soft waterusually gives better results and is preferred. The additives describedabove. when used. may be admixed with the water in the quantityrecommended in accordance with prior art practices, such as 4-2 cups ofsurface active agent for each 5-20 gallons of water. However. thecatalyst of the invention increases the effectiveness of a givenquantity of surface active agent or other additive and the amountrequired to produce equally satisfactory results is usually aboutone-eighth to one-half of that normally required. and often aboutone-fourth as much. as is used in prior art dish washing compositions.

The catalyst is present in the aqueous composition in a catalyticquantity which results in the desired im' provement. Usually thecatalyst is present in an amount of about 0.0000l-O.l weight percent.and preferably about 0.00040.00l weight percent of the aqueouscomposition. but larger or smaller amounts may be present as it is onlynecessary to provide the catalyst in catalytic amount. The aqueouscomposition may be prepared by diluting the aqueous suspension of thecatalyst as produced by the process described herein. In such instances.the aqueous suspension of catalyst as produced may be diluted with aboutlO0-l0,000 volumes of water and then used. For better results. theaqueous suspension of catalyst as produced may be diluted with about250-2000 parts of water before use,

and for still better results it may be diluted with about 500-1000 partsby weight of water before use. A sur face active agent and/or a watersoftening agent may be added thereto in the above described quantitieswhen desired.

Alternatively. when the aqueous composition contains a surface activeagent, the catalyst may be added to commercially available solid orliquid surface active compositions such as Cascade. lvory Snow. Tide andThrill. or to the surface active compositions disclosed in the patentslisted herein. The catalyst is present in a quantity to provide acatalytic amount when the commercial surface active composition isadmixed with water in the recommended ratio to wash dishes. Usually thecatalyst is present in an amount to provide about 0.0000l-O.l weightpercent, and preferably about 00004-000] weight percent in the waterthat is added thereto at the time of use. Often the catalyst is presentin an amount of about 0.0l-l weight percent based upon the weight of theconcentrated surface active composition. Larger or smaller amounts maybe present as it is only necessary to provide the catalyst in catalyticamounts in the aqueous composition prepared by diluting the surfaceactive composition with water.

It is not necessary to use special dish washing procedures or'equipmentand prior art hand washing and machine washing techniques are equallyeffective in the presence of the catalyst. Ordinary small householdautomatic dish washing machines are preferred for household use. andlarge industrial dish washing machines for larger scale use such as inrestaurants, hospitals and other institutions. It also is not necessaryto change the surface active agent. the amount or ratio of water andsurface active agent. the dish washing cycle, or other operatingprocedure with the exception of adding the catalyst. However. often itis preferred to use much less surface active agent to obtain equallysatisfactory results and/or to allow the culinary articles to soak inwater containing the catalyst and/or surface active agent prior tocommencing the washing cycle. The soaking action is especially effectiveas it allows the catalyst to break the bond between the tightly adheringfood particles and the surface of the culinary articles before thewashing cycle begins and often a surface active agent is not needed. Theculinary articles may be soaked. for example. for about five minutes toseveral hours and preferably for about 15 minutes to 1 hour. The dishwashing cycle for an automatic dish washer may be. for example, a periodof about 5-30 minutes and preferably about 10-20 minutes.

The catalyst markedly speeds up the cleaning action and allows the foodparticles, stains and other foreign substances to be removed from thesurface of the culinary articles in a minimum period of time and withminimum effort. Cold water is satisfactory and it is not necessary touse warm or hot water. The catalyst is especially effective in theremoval of tightly adhering dried intially liquid or semi-liquid filmsand particles of food and burned or thermally decomposed food. In suchinstances. the catalyst seems to loosen the bond between the surface ofthe culinary articles and the foreign substances. thereby allowing theforeign substances to be easily removed. The catalyst does not containnitrogen or phosphorous compounds and it is non-polluting. The catalystalso aids in the uniform and complete removal of food stains. films,streaks and residues in general and the washed and dried culinaryarticles are very pleasing in appearance. Colored designs on dishes andother culinary articles are not harmed and the catalyst does notchemically attack metallic culinary articles such as pots. pans. knives.forks, spoons and the like.

The catalyst used in practicing the present invention is unique and hasmany unusual and unexpected properties. It is presently thought thatthese unusual and unexpected properties result from the way the catalystis prepared. and thus it should be prepared following the processdescribed hereinafter.

PREPARATION OF THE CATALYST The catalyst used in practicing the presentinvention may be prepared as described below. In the presently preferredprocess for preparing an aqueous suspension of the catalyst, a watersoluble alkali metal silicate is admixed and reacted with an aqueoussolution of a water soluble dissolved substance which is a source ofcalcium ion and a water soluble dissolved substance which is a source ofmagnesium ion to produce a finely divided or colloidal suspension of thereaction product. The aqueous solution contains the dissolved substancesinitially in amounts to provide between about 1 X and l X 10 mole perliter each of calcium ion and magnesium ion, preferably between about 1X 10 and l X 10' mole per liter, and for still better results between 1X 10 and 6 X 10 mole per liter. The dissolved substances should also bepresent in amounts to provide a molar ratio of calcium ion to magnesiumion between about 201.0 and l.0:2.0, and preferably about 1.5: l .0 and10:15. For best results, the aqueous medium should contain the dissolvedsubstances in amounts to provide between about 2.5 X 10 and 3.0 X 10mole per liter each of calcium ion and magnesium ion, and the molarratio of calcium ion to magnesium ion should be about l.0:l.0, e.g., 2.9X l0 mole per liter of calcium ion and 2.7 X 10 mole per liter ofmagnesium ion. The alkali metal silicate should have an alkali metaloxide to silicon dioxide ratio between about 0.9:].0 and less than2.0:l.0, and preferably between about 0.9:l.0 and l.2:l.0. The alkalimetal silicate should be admixed with the aqueous medium in an amount ofabout 0.05-2 moles per liter. preferably about 0.1-1 mole per liter, andfor still better results about 0.2-0.5 mole per liter. For best results,the alkali metal silicate should be an alkali metal metasilicate havingan alkali metal oxide to silicon dioxide ratio of about l:l. and itshould be admixed with the aqueous medium in an amount to provide about0.2-0.3 mole per liter, e.g., about 0.25 mole per liter.

Examples of sources of calcium ion and magnesium ion for use inpreparing the aqueous solution include mineral acid salts such as thehalides, sulfates, bisulfates. nitrites, and nitrates of calcium andmagnesium. The chlorides are usually the preferred halides, and bothcalcium and magnesium chloride are soluble and may be used. Magnesiumsulfate and bisulfate are soluble and often are the preferred sources ofmagnesium ion. Calcium sulfate is only slightly soluble in water andusually is not a preferred source ofcalcium ion, but calcium bisulfateis somewhat more soluble. While calcium and magnesium nitrite or nitrateare soluble in water and may be used, these substances are not preferredin most instances. The sources of calcium ion and magnesium ion aredissolved in the aqueous medium in amounts to provide calcium ion andmagnesium ion within the above ranges. Complete ionization is assumedwhen calculating the quantities to be dissolved and any desired order ofaddition is satisfactory. For example, the source of calcium ion may beadded to the aqueous medium before, during or after the source ofmagnesium ion.

The alkali metal silicate to be admixed with the aqueous medium ispreferably a water soluble sodium or potassium silicate having an alkalimetal oxide (M 0) to silicon dioxide (SiO mole ratio between about 0.9:1.0 and less than 2.0110, and preferably between about 0911.0 and1211.0. The best results are usually obtained with an alkali metalmetasilicate having an alkali metal oxide to silicon dioxide ratio ofabout l:l. Hydrated alkali metal silicates dissolve faster and should beused for best results when the alkali metal silicate is added in solidform. In instances where an anhydrous alkali metal silicate is used, itmay be desirable to dissolve it in water and then add the solution tothe aqueous medium. Sodium metasilicate is preferred and usually ahydrated sodium metasilicate such as the pentahydrate gives the bestresults.

Carbonate ion and/or bicarbonate ion should not be present in theaqueous medium in substantial concentrations as the calcium ion andmagnesium ion are precipitated in the form of their respectivecarbonates. The free carbonate ion and/or bicarbonate ion concentrationsin the aqueous medium should not exceed about 10 parts per million byweight based upon the combined weight of the water and the ingredientsadded thereto and for this reason, the alkali metal silicates should besubstantially free of carbonate ion and bicarbonate ion. A small amountof precipitated calcium carbonate and/or magnesium carbonate may bepresent in the aqueous medium provided additional calcium ion andmagnesium ion are available to meet the above defined concentrations.

Distilled water and/or deionized water are usually preferred over anatural or untreated water when preparing the aqueous medium. Ininstances where water is used which contains substantial initialconcentrations of alkaline earth metal ions, then this should be takeninto consideration in calculating the amounts of the sources of calciumion and magnesium ion which are necessary to arrive at the finalconcentrations previously discussed.

An electrolyte which aids in the preparation of colloidal suspensionsmay be present in the aqueous medium at the time of admixing the alkalimetal silicate therewith. Examples of electrolytes include those used inpreparing prior art colloidal suspensions such as the alkali metalhalides, sulfates and bisulfates. Sodium chloride, sodium sulfate andsodium bisulfate are usually preferred. The electrolyte should be addedin small amounts such as, for example, about 0.00001-0.l mole per liter,but often larger or smaller amounts may be present.

The conditions under which the alkali metal silicate is admixed with theaqueous medium and reacted with the sources of calcium ion and magnesiumion are not critical provided the reaction mixture is maintained in theliquid phase. The reaction temperature may be, for example, between thefreezing point and boiling point of water under the existing pressureconditions. At atmospheric pressure, the temperature is usually aboutl0-90C and often a more convenient temperature is about 2050C. In manyinstances, ambient or normal room temperature is satisfactory.

The degree of agitation is not critical. and mild to vigorous agitationmay be employed during addition of the alkali metal silicate. For thebest results, the aqueous medium should be agitated sufficiently toassure rapid and uniform admixing of the alkali metal silicate. Aftercompleting the addition of the alkali metal silicate, when desired theagitation may be continued for a sufficient period of time to assurecomplete reaction and aging of the resulting colloidal suspension. suchas for approximately 1-5 minutes to 1 hour or longer.

Upon admixing the alkali metal silicate with the aqueous medium, ittakes on a turbid appearance but in most instances no significant amountof visible precipitate is formed. The colloidal suspension of thereaction product thus produced should be strongly basic and may have apH value of, for example. approximately 4 and preferably about 1 l-l 3,and for best results about 12. In view of this. the initial pH value ofthe aqueous medium containing the dissolved sources of calcium ion andmagnesium ion is of importance and should be about 6-9 and preferablyabout 7-8. When necessary. it is possible to adjust the pH value of theaqueous medium to the foregoing levels either before during or afteraddition of the alkali metal silicate by adding bases such as sodium orpotassium hydroxide, or mineral acids such as sulfuric or hydrochloricacid.

The colloidal suspension may be stored for several weeks or longer whileawaiting the further treatment described hereinafter. ln instances wherethe colloidal suspension is to be stored over a substantial period oftime, the pH value should be maintained at the above described level andthe storage vessel is preferably a tightly capped polyethylene bottle orother inert plastic container which prevents the contents from absorbingcarbon dioxide from the atmosphe The colloidal suspension of the:sactior product is not suitable for use as a catalyst as prepared andit should be agitated sufficiently in the presence of a micelle-formingsurfactant to form catalyst-containing micelles. The degree ofagitation. the length of the agitation period, and the amount of themicelie-forr surfactant that is present in the colloidal seep: ioncontrolled at levels favorable to the formation m. celles. For example.the surfactant may be present in an amount of about 0.00l-0.l mole perliter and preferably about 0.03-0.07 mole per liter for mostsurfactants. Smaller or larger amounts may be effective with somesurfactants such as 0.0001 mole per l ter or less. or 2 mole per literor more. About 0.05 mi. *er liter :1 gives the best results with manysurfactants.

The minimum period of agitation and the minimum degree of agitation.that are required for micelle formation varies somewhat withtemperature and the type and amount of surfactant. As is well understoodin this art, gradually increasing these variants in the presence of aneffective amount of the micelle-forming surfactant will result inmicelle formation when the proper levels are reached. As a general rule.longer periods of agitation and/or more vi; .ns agitation are requiredto form micelles at lower neratures approaching the freezing point ofthe COllOlu =1 suspension than at higher temperatures approaching theboiling point. 1n instances where the aqueous suspension has atemperature of approximately 50-90C., then mild agitation over a periodof about 10-60 minutes is satisfactory. Often longer or shorter periodsof mild to vigorous agitation may be employed such as from about 1-5minutes to several hours at temperatures varying, respectively. betweenthe boiling point and the freezing point. When desired, the agitationmay be continued long after the catalyst-containing micelles are formedas continued agitation does not seem to have an adverse affect.

As a general rule. the micelle-forming surfactants known in the priorart may be used in practicing the present invention. Micelle-formingsurfactants used in the emulsion polymerization of monomeric organiccompounds are disclosed in the text Synthetic Rubber, by G. 5. Whitby,et al., John Wiley & Sons Incorporated. New York (1954), and surfaceactive agents in general are disclosed on pages 418-424 of the textOrganic Chemistry, Fieser and Fieser, 2nd Edition, Reinhold PublishingCorporation, New York, New York (1950), the disclosures of which areincorporated herein by reference. Examples of surfactants disclosed inthe above texts include the alkali metal soaps of long chain fattyacids, and especially the sodium and potassium soaps of fatty acidscontaining about 14-25 carbon atoms and preferably about 16-18 carbonatoms, and the sodium and potassium soaps of the rosin acids, abieticacid and the derivatives thereof. Other micelle forming surfactantsinclude fats and oils such as corn oil, cotton seed oil, castor oil, soybean oil and safflower oil which have been fully or partially saponifiedwith alkali metal bases to produce mixtures including saponified longchain fatty acids, the monoor diglycerides thereof, and glycerin.

Examples of synthetic micelle-forming surfa zn'ts include the sulfonatesof long chain alcohols prepawzd by hydrogenation of naturally ocurringfats and oils of the above types and especially sulfonated long chainalcohols containing about 10-20 and preferably about 12-14 carbon atoms,the alkali metal salts of the monosulfonates of monoglycerides such assodium glyeetyl monolaurate sulfonate, the sulfonates of succinic acidesters such as dioctyl sodium sulfosuccinate and the alkylaryl alkalimetal sulfonates. Specific examples of presently preferredmicelle-forming surfactants include sodium and potassiumsulforicinoleate, tetrahydronaphthalene sulfonate, octahydroanthracenesulfonic acid, butyl naphthalene sulfonic acid, sodium xylene sulfonate,alkyl benzene sulfonic acid and potassium benzene sulfonate.

Sulfated long chain hydroxycarboxylic acids containing about 14-25carbon atoms and preferably about 16-18 carbon atoms, and sulfated fatsand oils containing hydroxycarboxylic acids of this type produceexceptionally good micelle-forming surfactants. At least 25% of thehydroxyl groups and preferably at least 50% should be sulfated, and upto 95-100% may be sulfated. It is usually preferred that the sulfatedoils and/or long chain hydroxycarboxylic acids be neutralized with analkali metal base, and that the corresponding alkali metal salts beadded to the colloidal suspension in the form of an aqueous solution.The aqueous solution may contain at least 25% of water and preferably atleast 35-40% by weight. Much larger percentages of water may be presentwhen desired such as -80% or more by weight.

A very active catalyst is produced when using sulfated castor oil as themicelle-forming surfactant (Turkey Red oil.) Sulfated castor oil whichhas been purified sufficiently to be of U.S.P. or medicinal gradeproduces an exceptionally active catalyst. For the best results, thecastor oil is reacted with about an equal weight of concentratedsulfuric acid (e.g., 20% by weight) at a temperature of approximately2530C. The mixture may be reacted for about two hours with stirring andis then neutralized with sodium hydroxide solution. The reaction mixtureseparates into three layers, i.e.. an upper layer which is a watersolution, an intermediate or oily layer, and a white curdy precipitate.The intermediate oily layer is separated from the upper and lowerlayers, and may be added to the colloidal suspension as themicelle-forming surfactant in an amount, for example of 0001-01 mole perliter, and preferably about 0.005 mole per liter.

The activity of the catalyst may be increased very centration in thequantities previously discussed. The weight of the catalyst iscalculated on a dry solids basis, i.e., the weight of the catalystingredients in the aqueous suspension as produced after removal of thewater.

The invention is further illustrated by the following specific examples.

EXAMPLE 1 This example illustrates one presently preferred process forpreparing the novel catalyst used in practicing the invention.

Anhydrous calcium chloride in' an amount of 0.66 gram and magnesiumsulfate heptahydrate in an amount of 1.32 grams were dissolved in twoliters of demarkedly by cooling the aqueous catalyst suspension toionized water with stirring and warming until solution a temperatureapproaching the freezing point such as was Complete- 95 grams of Sodiumsilicate P about 1 0 and the Warming Over one or more hydrate having amolecular ratio of sodium oxide to silcycles. For best results, theaqueous catalyst suspension lffon dloxlde 9 131 were added to thesolution'wlth Stiff should be frozen and thawed over one or more cycles.and cofltmued Warmmg to Produce a whlte c0110 The reason for theincreased catalytic activity is not dal suspenslon of the reflcnonproduct; fuuy understood at Ihe present time but Cooling and Aftersetting for 1 0 minutes, the colloidal suspension then warming theaqueous catalyst suspension seems to was heated to 80 and sulfatfad 9 man increase the concentration of the catalyst-containing amount of 201grams was added wlth Snmng' The aver micelles and/or increases thecatalytic activity thereof. age moleculfir welght of the sulfated was940 The aqueous Suspension of the catalyst Contains a rel and itcontained 50% of water. The turbidity lessened somewhat as the colloidalsuspension was heated at atively small percentage by weight of theactive catalyst 0 0 for 1 hour with vigorous stirring to produce asproduimd' when. deslred It may be concentrated by catalyst micelles. Theaqueous suspension of catalyst a P of the to a micelles thus preparedhad a viscosity similar to that of centrated hqud Catalyst susPenslon Wbe water and it was used as the catalyst in certain Examstored and usedmore conveniently. It 15 also possible ples as noted hereinafter. toprepare a dry catalyst concentrate by evaporating A dry or SolidCatalyst Concentrate was prepared in substantially all of the water. Thepreferred method of a further run by evaporating water from theinitially producing the dry catalyst concentrate 18 by flashevapprepared aqueous catalyst Suspension The resulting f u 5ingtechnique. analogous to that employed dry catalyst concentrate wasresuspended in water and Prepurmg Powdered mllk- The Catalystconcentrates there was no substantial loss of catalytic activity. Instill Produced "P Partial or complete evaporation of the other runs, thecatalytic activity of the aqueous suspen- Waler Content of the lmlallyPrepared aqueous Suspen sion of catalyst as initially prepared, thediluted aque- Slon may be reconstituted Of Water ous uspension ofcatalyst and the reconstituted aque. tle or no loss of catalyticactivity. Preferably, the water ous catalyst suspension was enhanced byf i and is added to the dry catalyst concentrate under suffithawingciently vigorous conditions of agitation to assure that the catalystmicelles are resuspended and uniformly EXAMPLE H distributed. Thisexample illustrates the preparation of additional The aqueous catalystsuspension may be used as procatalyst suspensions duced in Practicingthe invention, but Preferably it is Five suspensions of the catalystwere prepared from d u e With PP Y 10040900 Parts y Weight the sameingredients as used in Example 1 and following of water and then used.For better results, the catalyst h general ed e of Exam le I, The ratioof insuspension should be diluted with about 250-2,000 di m w varied asfollows;

Ingredient Amount of Ingredient Run 1 Run 2 Run 3 Run 4 Run 5 Deionizedwater 2 1 1.5 l 1.5 l 1.5 l 0.25 l CaCl; 0.66 g 0.5 g 0.5 g 1.0 g 0.5 gMgSO .7H O 1.32 g 1.0 g 1.0 g 2.0 g 1.0 g Na- -SiO .5H O 165 g 132 g 71g 185 g 71 g Sulfated Castor ml ml 150 ml 200 m1 150 ml oil(approximately 5071 by weight H O) The catalyst suspensions prepared bythe above five runs were used in certain examples as noted hereinafter.

EXAMPLE 111 This example illustrates the use of a catalyst prepared inaccordance with Example 1 in washing dishes. A

standard household automatic dishwasher was used in this Example.

In the first run, an attempt was made to remove food particles fromsoiled dishes using a commercially available dish washing detergent. Therecommended amount of detergent and the recommended washing cycle wasused. In a second run. the same procedure was used as in the first runwith the exception of also adding approximately six fluid ounces of thecatalyst suspension. Otherwise. the second run was identical with thefirst run.

The dishes washed in the first run in the absence of the catalyst hadsome food particles adhering to the surface and also had a noticeablefilm thereon. The dishes washed in the second run using the catalystwere much cleaner and free of food particles, and dried without leavinga noticeable soap film.

EXAMPLE IV The general procedure of Example I" was repeated in a seriesof runs with the exception of reducing the amount of dishwashingdetergent to between one-half and one-eighth of the recommended amountemployed in Example lll. It was found that about I A as much dishwashing detergent is required to obtain equally satisfactory resultswhen washing dishes in the presence of a catalytic amount of thecatalyst.

EXAMPLE V The general procedures of Examples III and IV are repeated ina further series of runs with the exception of using the catalystsprepared in accordance with Example II. The Example ll catalysts areactive and produce comparable results.

EXAMAPLE VI The general procedure of Example III was repeated with theexception of washing the dishes by hand. The results obtained in thisExample are substantially the same as those of Example III. The disheswashed in the run using the catalyst are cleaner. brighter and are freeof food particles. When the dishes were washed in the absence of thecatalyst, much more effort was required to remove dried food particlesand also the dishes did not appear to be as clean and bright due to aresidual surface film.

EXAMPLE VII This Example illustrates the use of only a diluted catalystsuspension in washing dishes.

A catalyst suspension was prepared in accordance with Example I anddiluted with 1.000 volumes of water. The resulting diluted catalystsuspension was used in washing soiled culinary articles includingdishes. knives. forks. spoons. pots and pans. The culinary articles weresoaked in the diluted catalyst suspension for approximately minutes toloosen the bond between the food particles and the surface of theculinary articles, and were then washed by hand. Very little effort wasrequired to remove the food particles and the culinary articles driedbright and free of a residual film.

In a further run. pots having a tightly adherent layer of scorched foodtherein were soaked for IS minutes in the diluted catalyst suspensionand then scrubbed. The 6 little effort. Only a light scrubbing actionwas necessary to remove the scorched food layer. In a similar run in theabsence of the catalyst. several minutes of hard work was required witha conventional dish washing detergent.

EXAMPLE VIII A catalyst suspension was prepared in accordance withExample I and the water content was evaporated to produce a driedcatalyst concentrate.

The dried catalyst concentrate is admixed with a commercially availabledish washing detergent (Cascade) in an amount of 1% by weight. Theresulting admixture of catalyst and detergent is used in one series ofruns to wash soiled dishes with dried food particles thereon in astandard household automatic dishwasher. In a second series of runswhich are otherwise identical, the catalyst is omitted and only theinitial commercial detergent formulation is used. The recommended amountof detergent and the recommended washing cycle is used in each series ofruns.

The dishes washed in the series of runs using the catalyst are muchcleaner and are free of food particles. The dishes from these runs alsodry without leaving a noticeable soap film. The dishes washed in theabsence of the catalyst have some food particles adhering to thesurfaces. The dry dishes also have a noticeable film thereon.

I claim:

I. A method of washing soiled culinary articles having food depositsadhering to the surface thereof comprising intimately contacting thesoiled culinary articles with water containing an effective amount of acatalyst until at least a portion of the said food deposits are removedfrom the surface thereof,

the catalyst being prepared by a process comprising admixing a watersoluble alkali metal silicate with an aqueous medium containing adissolved substance which provides calcium ions in the aqueous mediumand a dissolved substance which provides magnesium ions in the aqueousmedium,

the aqueous medium containing said dissolved substances in amounts toprovide a total concentration in the aqueous medium of between about 1 X10 and l X 10 mole per liter each of calcium ions and magnesium ions,

the aqueous medium containing said dissolved substances in amounts toprovide a molar ratio of calcium ions to magnesium ions between about2.0:l.O and l.0:2.0,

the alkali metal silicate having an alkali metal oxide to silicondioxide ratio between about O.9:l.0 and less than 2.0: l .0 and beingadmixed with the aqueous medium in an amount of about 0.05-2 moles perliter.

reacting the alkali metal silicate with said dissolved substancesproviding calcium ions and magnesium ions to produce an aqueoussuspension of finely divided particles of the reaction product,

admixing a micelle-forming surfactant with the aqueous medium in anamount to form catalyst micelles including said finely divided particlesof the reaction product upon agitating the aqueous medium, and

agitating the aqueous medium containing said finely divided particles ofthe reaction product and surfactant to form said catalyst micelles,

the said resulting aqueous medium being diluted with at least l volumesof water prior to washing the soiled culinary articles therein and thesaid catalyst micelles being present therein in a concentrationeffective to promote the removal of the said food deposits.

2. The method of claim 1 wherein in the process for preparing thecatalyst. said ratio of calcium ions to magnesium ions is between about1.5110 and 1.0:l.5.

3. The method of claim 1 wherein in the process for preparing thecatalyst, said ratio of calcium ions to magnesium ions is about 10:10.

4. The method of claim 1 wherein in the process for preparing thecatalyst, the alkali metal silicate is admixed with an aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcentration in the aqueous medium of between about 1 X l0 and 6 X [0*mole per liter each of calcium ions and magnesium ions.

5. The method of claim 1 wherein in the process for preparing thecatalyst. the alkali metal silicate is admixed with an aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcentration in the aqueous medium of between about 2.5 X l0 and 3.0 Xl0 mole per liter each of calcium ions and magnesium ions.

6. The method of claim 1 wherein in the process for preparing thecatalyst, about 0.20.5 mole per liter of the alkali metal silicate isadmixed with the aqueous medium.

7. The method of claim 1 wherein in the process for preparing thecatalyst, the alkali metal silicate has an alkali metal oxide to silicondioxide ratio between about 09:10 and l.2:l.0.

8. The method of claim 1 wherein in the process for preparing thecatalyst, the alkali metal silicate is alkali metal metasilicate havingan alkali metal oxide to silicon dioxide ratio of about l.O:l.0.

9. The method of claim 1 wherein in the process for preparing thecatalyst. about 0.0l0.1 mole per liter of the surfactant is admixed withthe aqueous medium.

10. The method of claim 1 wherein in the process for preparing thecatalyst, the surfactant comprises sulfated castor oil.

11. The method of claim 1 wherein in the process for preparing thecatalyst, the alkali metal silicate is admixed with an aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcentration in the aqueous medium of between about 1 X 10*" and 6 X 10mole per liter each of calcium ions and magnesium ions, the ratio ofcalcium ions to magnesium ions is between about 1.5: l .0 and 1.0: 1.5,about 0.20.5 mole per liter of the alkali metal silicate is admixed withthe aqueous medium, and the alkali metal silicate has an alkali metaloxide to silicon dioxide ratio between about 0.9: and 1.2110.

12. The method of claim 1 wherein in the process for preparing thecatalyst. the alkali metal silicate is ad mixed with an aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcen tration in the aqueous medium of between about 2.5 X 10* and 3.0X 10 mole per liter each of calcium ions and magnesium ions. the aqueousmedium contains about equimolar amounts of calcium ions and magnesiumions, about 0.2-0.3 mole per liter of the alkali metal silicate isadmixed with the aqueous medium, and the alkali metal silicate has analkali metal oxide to silicon dioxide ratio of about l.O:l.0.

13. The method of claim 12 wherein in the process for preparing thecatalyst, the alkali metal metasilicate is sodium metasilicate having analkali metal oxide to silicon dioxide ratio of about l.O:l.0.

14. The method of claim 12 wherein in the process for preparing thecatalyst. about 0.0 1-0.1 mole per liter of the surfactant is admixedwith the aqueous medium.

15. The method of claim 14 wherein in the process for preparing thecatalyst, the surfactant comprises sulfated castor oil.

16. The method of claim 15 wherein in the process for preparing thecatalyst, the alkali metal metasilicate is sodium metasilicate having asodium oxide to silicon dioxide ratio of about 11011.0

17. The method of claim 16 wherein in the process for preparing thecatalyst, at least 25% of the hydroxy groups of the castor oil aresulfated, and about 0.03-0.07 mole per liter of the sulfated castor oilis admixed with the aqueous medium.

18. The method of claim 12 wherein in the process for preparing thecatalyst, the alkali metal silicate is admixed with an aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcentration in the aqueous medium of about 2.9 X 10* mole per liter ofcalcium ions and about 2.7 X 10 mole per liter of magnesium ions, about0.25 mole per liter of sodium metasilicate having a sodium oxide tosilicon dioxide ratio of about 10:10 is admixed with the aqueous medium,the aqueous medium contains not more than 10 parts per million by weightof carbonate ions and bicarbonate ions, the surfactant comprisessulfated castor oil and at least 50% of the hydroxy groups of the castoroil are sulfated, and about 0.05 mole per liter of the sulfated castoroil is admixed with the aqueous medium.

19. In a method of washing soiled culinary articles wherein the culinaryarticles are intimately contacted with an aqueous composition containingwater and an active ingredient comprising at least one material selectedfrom the group consisting of l a surface active agent and (2) acombination of a surface active agent and a water softening agent, theculinary articles having food deposits thereon and being intimatelycontacted with the aqueous composition under conditions whereby at leasta portion of the said food deposits are removed,

the improvement in combination therewith comprising intimatelycontacting the soiled culinary articles with the said aqueouscomposition in the presence of an effective amount of a catalyst,

the catalyst being prepared by a process comprising admixing a watersoluble alkali metal silicate with an aqueous medium containing adissolved substance which provides calcium ions in the aqueous mediumand a dissolved substance which provides magnesium ions in the aqueousmedium,

the aqueous medium containing said dissolved substances in amounts toprovide a total concentration in the aqueous medium of between about 1 X10 and l X 10 mole per liter each of calcium ions and magnesium ions,

the aqueous medium containing said dissolved substances in amounts toprovide a molar ratio of calcium ions to magnesium ions between about2.0.1.0 and l.0:2.0,

the alkali metal silicate having an alkali metal oxide to silicondioxide ratio between about 0921.0 and less than 2.0.1.0 and beingadmixed with the aqueous medium in an amount of about 0.05-2 moles perliter,

reacting the alkali metal silicate with said dissolved substancesproviding calcium ions and magnesium ions to produce an aqueoussuspension of finely divided particles of the reaction product,

admixing a micelle-forming surfactant with the aqueous medium in anamount to form catalyst micelles including said finely divided particlesupon agitating the aqueous medium. and

agitating the aqueous medium containing the said finely dividedparticles and surfactant to form said catalyst micelles,

the said resulting aqueous medium being diluted with at least lOOvolumes of water prior to washing the soiled culinary articles thereinand the said catalyst micelles being present therein in a concentrationeffective to promote the removal of the said food deposits.

20. The method of claim 19 wherein the said active ingredient of theaqueous composition comprises a major proportion of a mixture of (a) atleast one surface active agent, and (b) at least one water softeningagent.

21. The method of claim 19 wherein in the process for preparing thecatalyst. said ratio of calcium ions to magnesium ions is between aboutl.5:l.0 and 10:15.

22. The method of claim 19 wherein in the process for preparing thecatalyst, said ratio of calcium ions to magnesium ions is about l.0:l.0.

23. The method of claim 19 wherein in the process for preparing thecatalyst, the alkali metal silicate is admixed with an aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcentration in the aqueous medium of between about 1 X 10 and 6 X 10""mole per liter each of calcium ions and magnesium ions.

24. The method of claim 19 wherein in the process for preparing thecatalyst. the alkali metal silicate is admixed with an aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcentration in the aqueous medium of between about 2.5 X 10 and 3.0 XlO mole per liter each of calcium ions and magnesium ions.

25. The method of claim 19 wherein in the process for preparing thecatalyst. about 0.2-0.5 mole per liter of the alkali metal silicate isadmixed with the aqueous medium.

26. The method of claim 19 wherein in the process for preparing thecatalyst, the alkali metal silicate has an alkali metal oxide to silicondioxide ratio between about 0.9:].0 and l.2:l.0.

27. The method of claim 19 wherein in the process for preparing thecatalyst. the alkali metal silicate is alkali metal metasilicate havingan alkali metal oxide to silicon dioxide ratio of about l.0:l.0.

28. The method of claim 19 wherein in the process for preparing thecatalyst, about 0.0 l0. l mole per liter of the surfactant is admixedwith the aqueous medium.

29. The method of claim 19 wherein in the process for preparing thecatalyst. the surfactant comprises sulfated castor oil.

30. The method of claim 19 wherein in the process for preparing thecatalyst, the alkali metal silicate is admixed with an aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcentration in the aqueous medium of between about 1 X 10 and 6 X 10mole per liter each of calcium ions and magnesium ions, the ratio ofcalcium ions to magnesium ions is between about 1.5: l .0 and 1.0: l .5,about 0.2-0.5 mole per liter of the alkali metal silicate is admixedwith the aqueous medium, and the alkali metal silicate has an alkalimetal oxide to silicon dioxide ratio between about 09:10 and l.2:l.0.

31. The method of claim 19 wherein in the process for preparing thecatalyst. the alkali metal silicate is admixed with an aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcentration in the aqueous medium of between about 2.5 X l0 and 3.0 Xl0' mole per liter each of calcium ions and magnesium ions, the aqueousmedium contains about equimolar amounts of calcium ions and magnesiumions, about 0.20.3 mole per liter of the alkali metal silicate isadmixed with the aqueous medium, and the alkali metal silicate has analkali metal oxide to silicon dioxide ratio of about l.0:l.0.

32. The method of claim 31 wherein in the process for preparing thecatalyst, the alkali metal metasilicate is sodium metasilicate having analkali metal oxide to silicon dioxide ratio of about l.0:l.0.

33. The method of claim 31 wherein in the process for preparing thecatalyst, about 0.0 1-0.1 mole per liter of the surfactant is admixedwith the aqueous medium.

34. The method of claim 33 wherein in the process for preparing thecatalyst, the surfactant comprises sulfated castor oil.

35. The method of claim 34 wherein in the process for preparing thecatalyst, the alkali metal metasilicate is sodium metasilicate having asodium oxide to silicon dioxide ratio of about l.0:l.0.

36. The method of claim 35 wherein in the process for preparing thecatalyst, at least 25% of the hydroxy groups of the castor oil aresulfated, and about 0.03-0.07 mole per liter of the sulfated castor oilis admixed with the aqueous medium.

37. The method of claim 36 wherein in the process for preparing thecatalyst, the alkali metal silicate is admixed with an aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcentration in the aqueous medium of about 2.9 X 10 mole per liter ofcalcium ions and about 2.7 X 10 mole per liter of magnesium ions, about0.25 mole per liter of sodium metasilicate having a sodium oxide tosilicon dioxide ratio of about 10:10 is admixed with the aqueous medium,the aqueous medium contains not more than 10 parts per million by weightof carbonate ion and bicarbonate ion, the surfactant comprises sulfatedcastor oil and at least 50% of the hydroxy groups of the castor oil aresulfated, and about 0.05 mole per liter of the sulfated castor oil isadmixed with the aqueous medium.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3, 874,927 DATED April 1, 1975 O (S) John W. Willard, SI.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 7, Line 35, read the last word as "atmosphere";

Line 36, read the words between "of" and product" as the reaction Line41, read the last word as micelle-forming";

Line 42, read all after "colloidal" as suspension are Line 43, read allafter "the" as formation of mi- Line 44, read the word after "be" aspresent Line 48, read all after "per"'as liter or less,

Line 49, read all after 8.05" as mole per liter often Line 50, read thelast word as "surfactants;

Line 59, read the word after "more" as vigorous Line 6Q, read the wordsbetween "at" and "approaching" as lower temperatures and Line 61, readthe word before "suspension" as colloidal Column 8, Line 5, read thelast word as "adverse";

Line 9, read the word after "surfactants" as used Line 10, read the lastword as "organic"; Line 23, read the last word as "acids"; Line 29, readall after "mono" as or di- Line Bl, the last word as "surfactants"; Line32, read the last word as "prepared"; Line 33 read all after "and" asoils of Line 3%, read the last word as "chain";

. UNITED STATES PATENT OFFICE a 2 CERTIFICATE OF CORRECTION PATENT NO.

DATED April 1 a 181 5 |NVENTOR(5) I John '2?- Willard, SLY.

It is certified that error appears in the aboveidentified patent andthat said Letters Patent are hereby corrected as shown below:

Line 35, read the last word as "about"; Line 36, read the last word as"mono"; and Line 37, read the last word as "glyceryl";

Column 11, Line 24, change l 1/4" to one 1/4 55 8111'? ealee? this 24thday of June 15'75.

fittest:

C. MARSHALL DANN Commi ss ioner of Patent 5 and Trad emarks RUTH C.ZIASOIY Attesting Officer

1. A METHOD OF WASHING SOILED CULINARY ARTICLES HAVING FOOD DEPOSITSADHERING TO THE SURFACE THEREOF COMPRISING INTIMATELY CONTACTING THESOILED CULINARY ARTICLES WITH WATER CONTAINING AN EFFECTIVE AMOUNT OF ACATALYST UNTIL AT LEAST A PORTION OF THE SAID FOOD DEPOSITS ARE REMOVEDFROM THE SURFACE THEREOF, THE CATALYST BEING PREPARED BY A PROCESSCOMPRISING ADMIXING A WATER SOLUBLE ALKALI METAL SILICATE WITH ANAQUEOUS MEDIUM CONTAINING A DISSOLVED SUBSTANCE WHICH PROVIDES CALCIUMIONS IN THE AQUEOUS MEDIUM AND A DISSOLVED SUBSTANCE WHICH PROVIDESMAGNESIUM IONS IN THE AQUEOUS MEDIUM, THE AQUEOUS MEDIUM CONTAINING SAIDDISSOLVED SUBSTANCES IN AMOUNTS TO PROVIDE A TOTAL CONCENTRATION IN THEAQUEOUS MEDIUM OF BETWEEN ABOUT 1 X 10**-4 AND 1 X 10**-1 MOLE PER LITEREACH OF CALCIUM IONS AND MAGNESIUM IONS, THE AQUEOUS MEDIUM CONTAININGSAID DISSOLVED SUBSTANCES IN AMOUNTS TO PROVIDE A MOLAR RATIO OF CALCIUMIONS TO MAGNESIUM IONS BETWEEN ABOUT 2.0:1.0 AND 1.0:2.0, THE ALKALIMETAL SILICATE HAVING AN ALKALI METAL OXIDE TO SILICON DIOXIDE RATIOBETWEEN ABOUT 0.9:1.0 AND LESS THAN 2.0:1.0 AND BEING ADMIXED WITH THEAQUEOUS MEDIUM IN AN AMOUNT OF ABOUT 0.05-2 MOLES PER LITER, REACTINGTHE ALKALI METAL SILICATE WITH SAID DISSOLVED SUBSTANCES PROVIDINGCALCIUM IONS AND MAGNESIUM IONS TO PRODUCE AN AQUEOUS SUSPENSION OFFINELY DIVIDED PARTICLES OF THE REACTION PRODUCT, ADMIXING AMICELLE-FORMING SURFACTANT WITH THE AQUEOUS MEDIIUM IN AN AMOUNT TO FORMCATALYST MICELLES INCLUDING SAID FINELY DIVIDED PARTICLES OF THEREACTION PRODUCT UPON AGITATING THE AQUEOUS MEDIUM AND, AGITATING THEAQUEOUS MEDIUM CONTAINING SAID FINELY DIVIDED PARTICLES OF THE REACTIONPRODUCT AND SURFACTANT TO FORM SAID CATALYST MICELLES, THE SAIDRESULTING AQUEOUS MEDIUM BEING DILUTED WITH AT LEAST 100 VOLUMES OFWATER PRIOR TO WASHING THE SOILED CULINARY ARTICLES THEREIN AND THE SAIDCATALYST MICELLES BEING PRESENT THEREIN IN A CONCENTRATION EFFECTIVE TOPROMOTE THE REMOVAL OF SAID FOOD DEPOSITS.
 2. The method of claim 1wherein in the process for preparing the catalyst, said ratio of calciumions to magnesium ions is between about 1.5:1.0 and 1.0:1.5.
 3. Themethod of claim 1 wherein in the process for preparing the catalyst,said ratio of calcium ions to magnesium ions is about 1.0:1.0.
 4. Themethod of claim 1 wherein in the process for preparing the catalyst, thealkali metal silicate is admixed with an aqueous medium containing saiddissolved substances in amounts to provide a total concentration in theaqueous medium of between about 1 X 10 3 and 6 X 10 3 mole per litereach of calcium ions and magnesium ions.
 5. The method of claim 1wherein in the Process for preparing the catalyst, the alkali metalsilicate is admixed with an aqueous medium containing said dissolvedsubstances in amounts to provide a total concentration in the aqueousmedium of between about 2.5 X 10 3 and 3.0 X 10 3 mole per liter each ofcalcium ions and magnesium ions.
 6. The method of claim 1 wherein in theprocess for preparing the catalyst, about 0.2-0.5 mole per liter of thealkali metal silicate is admixed with the aqueous medium.
 7. The methodof claim 1 wherein in the process for preparing the catalyst, the alkalimetal silicate has an alkali metal oxide to silicon dioxide ratiobetween about 0.9:1.0 and 1.2:1.0.
 8. The method of claim 1 wherein inthe process for preparing the catalyst, the alkali metal silicate isalkali metal metasilicate having an alkali metal oxide to silicondioxide ratio of about 1.0:1.0.
 9. The method of claim 1 wherein in theprocess for preparing the catalyst, about 0.01-0.1 mole per liter of thesurfactant is admixed with the aqueous medium.
 10. The method of claim 1wherein in the process for preparing the catalyst, the surfactantcomprises sulfated castor oil.
 11. The method of claim 1 wherein in theprocess for preparing the catalyst, the alkali metal silicate is admixedwith an aqueous medium containing said dissolved substances in amountsto provide a total concentration in the aqueous medium of between about1 X 10 3 and 6 X 10 3 mole per liter each of calcium ions and magnesiumions, the ratio of calcium ions to magnesium ions is between about1.5:1.0 and 1.0:1.5, about 0.2-0.5 mole per liter of the alkali metalsilicate is admixed with the aqueous medium, and the alkali metalsilicate has an alkali metal oxide to silicon dioxide ratio betweenabout 0.9:1.0 and 1.2:1.0.
 12. The method of claim 1 wherein in theprocess for preparing the catalyst, the alkali metal silicate is admixedwith an aqueous medium containing said dissolved substances in amountsto provide a total concentration in the aqueous medium of between about2.5 X 10 3 and 3.0 X 10 3 mole per liter each of calcium ions andmagnesium ions, the aqueous medium contains about equimolar amounts ofcalcium ions and magnesium ions, about 0.2-0.3 mole per liter of thealkali metal silicate is admixed with the aqueous medium, and the alkalimetal silicate has an alkali metal oxide to silicon dioxide ratio ofabout 1.0:1.0.
 13. The method of claim 12 wherein in the process forpreparing the catalyst, the alkali metal metasilicate is sodiummetasilicate having an alkali metal oxide to silicon dioxide ratio ofabout 1.0:1.0.
 14. The method of claim 12 wherein in the process forpreparing the catalyst, about 0.01-0.1 mole per liter of the surfactantis admixed with the aqueous medium.
 15. The method of claim 14 whereinin the process for preparing the catalyst, the surfactant comprisessulfated castor oil.
 16. The method of claim 15 wherein in the processfor preparing the catalyst, the alkali metal metasilicate is sodiummetasilicate having a sodium oxide to silicon dioxide ratio of about1.0:1.0
 17. The method of claim 16 wherein in the process for preparingthe catalyst, at least 25% of the hydroxy groups of the castor oil aresulfated, and about 0.03-0.07 mole per liter of the sulfated castor oilis admixed with the aqueous medium.
 18. The method of claim 12 whereinin the process for preparing the catalyst, the alkali metal silicate isadmixed with an aqueous medium containing said dissolved substances inamounts to provide a total concentration in the aqueous medium of about2.9 X 10 3 mole per liter of calcium ions and about 2.7 X 10 3 mole perliter of magnesium ions, about 0.25 mole per liter of sodiummetasilicate having a sodium oxide to silicon dioxiDe ratio of about1.0:1.0 is admixed with the aqueous medium, the aqueous medium containsnot more than 10 parts per million by weight of carbonate ions andbicarbonate ions, the surfactant comprises sulfated castor oil and atleast 50% of the hydroxy groups of the castor oil are sulfated, andabout 0.05 mole per liter of the sulfated castor oil is admixed with theaqueous medium.
 19. In a method of washing soiled culinary articleswherein the culinary articles are intimately contacted with an aqueouscomposition containing water and an active ingredient comprising atleast one material selected from the group consisting of (1) a surfaceactive agent and (2) a combination of a surface active agent and a watersoftening agent, the culinary articles having food deposits thereon andbeing intimately contacted with the aqueous composition under conditionswhereby at least a portion of the said food deposits are removed, theimprovement in combination therewith comprising intimately contactingthe soiled culinary articles with the said aqueous composition in thepresence of an effective amount of a catalyst, the catalyst beingprepared by a process comprising admixing a water soluble alkali metalsilicate with an aqueous medium containing a dissolved substance whichprovides calcium ions in the aqueous medium and a dissolved substancewhich provides magnesium ions in the aqueous medium, the aqueous mediumcontaining said dissolved substances in amounts to provide a totalconcentration in the aqueous medium of between about 1 X 10 4 and 1 X 101 mole per liter each of calcium ions and magnesium ions, the aqueousmedium containing said dissolved substances in amounts to provide amolar ratio of calcium ions to magnesium ions between about 2.0:1.0 and1.0:2.0, the alkali metal silicate having an alkali metal oxide tosilicon dioxide ratio between about 0.9:1.0 and less than 2.0: 1.0 andbeing admixed with the aqueous medium in an amount of about 0.05-2 molesper liter, reacting the alkali metal silicate with said dissolvedsubstances providing calcium ions and magnesium ions to produce anaqueous suspension of finely divided particles of the reaction product,admixing a micelle-forming surfactant with the aqueous medium in anamount to form catalyst micelles including said finely divided particlesupon agitating the aqueous medium, and agitating the aqueous mediumcontaining the said finely divided particles and surfactant to form saidcatalyst micelles, the said resulting aqueous medium being diluted withat least 100 volumes of water prior to washing the soiled culinaryarticles therein and the said catalyst micelles being present therein ina concentration effective to promote the removal of the said fooddeposits.
 20. The method of claim 19 wherein the said active ingredientof the aqueous composition comprises a major proportion of a mixture of(a) at least one surface active agent, and (b) at least one watersoftening agent.
 21. The method of claim 19 wherein in the process forpreparing the catalyst, said ratio of calcium ions to magnesium ions isbetween about 1.5:1.0 and 1.0:1.5.
 22. The method of claim 19 wherein inthe process for preparing the catalyst, said ratio of calcium ions tomagnesium ions is about 1.0:1.0.
 23. The method of claim 19 wherein inthe process for preparing the catalyst, the alkali metal silicate isadmixed with an aqueous medium containing said dissolved substances inamounts to provide a total concentration in the aqueous medium ofbetween about 1 X 10 3 and 6 X 10 3 mole per liter each of calcium ionsand magnesium ions.
 24. The method of claim 19 wherein in the processfor preparing the catalyst, the alkali metal silicate is admixed with anaqueous medium containing said dissolved substances in amounts toprovide a total concentration in the aqueous medium of between about 2.5X 10 3 and 3.0 X 10 3 mole per liter each of calcium ions and magnesiumions.
 25. The method of claim 19 wherein in the process for preparingthe catalyst, about 0.2-0.5 mole per liter of the alkali metal silicateis admixed with the aqueous medium.
 26. The method of claim 19 whereinin the process for preparing the catalyst, the alkali metal silicate hasan alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and1.2:1.0.
 27. The method of claim 19 wherein in the process for preparingthe catalyst, the alkali metal silicate is alkali metal metasilicatehaving an alkali metal oxide to silicon dioxide ratio of about 1.0:1.0.28. The method of claim 19 wherein in the process for preparing thecatalyst, about 0.01-0.1 mole per liter of the surfactant is admixedwith the aqueous medium.
 29. The method of claim 19 wherein in theprocess for preparing the catalyst, the surfactant comprises sulfatedcastor oil.
 30. The method of claim 19 wherein in the process forpreparing the catalyst, the alkali metal silicate is admixed with anaqueous medium containing said dissolved substances in amounts toprovide a total concentration in the aqueous medium of between about 1 X10 3 and 6 X 10 3 mole per liter each of calcium ions and magnesiumions, the ratio of calcium ions to magnesium ions is between about1.5:1.0 and 1.0:1.5, about 0.2-0.5 mole per liter of the alkali metalsilicate is admixed with the aqueous medium, and the alkali metalsilicate has an alkali metal oxide to silicon dioxide ratio betweenabout 0.9:1.0 and 1.2:1.0.
 31. The method of claim 19 wherein in theprocess for preparing the catalyst, the alkali metal silicate is admixedwith an aqueous medium containing said dissolved substances in amountsto provide a total concentration in the aqueous medium of between about2.5 X 10 3 and 3.0 X 10 3 mole per liter each of calcium ions andmagnesium ions, the aqueous medium contains about equimolar amounts ofcalcium ions and magnesium ions, about 0.2-0.3 mole per liter of thealkali metal silicate is admixed with the aqueous medium, and the alkalimetal silicate has an alkali metal oxide to silicon dioxide ratio ofabout 1.0:1.0.
 32. The method of claim 31 wherein in the process forpreparing the catalyst, the alkali metal metasilicate is sodiummetasilicate having an alkali metal oxide to silicon dioxide ratio ofabout 1.0:1.0.
 33. The method of claim 31 wherein in the process forpreparing the catalyst, about 0.01-0.1 mole per liter of the surfactantis admixed with the aqueous medium.
 34. The method of claim 33 whereinin the process for preparing the catalyst, the surfactant comprisessulfated castor oil.
 35. The method of claim 34 wherein in the processfor preparing the catalyst, the alkali metal metasilicate is sodiummetasilicate having a sodium oxide to silicon dioxide ratio of about1.0:1.0.
 36. The method of claim 35 wherein in the process for preparingthe catalyst, at least 25% of the hydroxy groups of the castor oil aresulfated, and about 0.03-0.07 mole per liter of the sulfated castor oilis admixed with the aqueous medium.
 37. The method of claim 36 whereinin the process for preparing the catalyst, the alkali metal silicate isadmixed with an aqueous medium containing said dissolved substances inamounts to provide a total concentration in the aqueous medium of about2.9 X 10 3 mole per liter of calcium ions and about 2.7 X 10 3 mole perliter of magnesium ions, about 0.25 mole per liter of sodiummetasilicate having a sodium oxide to silicon dioxide ratio of about1.0:1.0 is admixed with the aqueous medium, the aqueous medium containsnot more than 10 parts per million by weigHt of carbonate ion andbicarbonate ion, the surfactant comprises sulfated castor oil and atleast 50% of the hydroxy groups of the castor oil are sulfated, andabout 0.05 mole per liter of the sulfated castor oil is admixed with theaqueous medium.